Influence of FRET, charge separation, and density of defect states on the improvement of UV light-driven photocatalytic activity of PMMA capped ZnO nanomaterials

Abstract

This study employs oxidative polymerization, co-precipitation, and ex-situ surface capping techniques to fabricate pristine PMMA, ZnO, and PMMA-capped ZnO specimens with varying PMMA concentrations. X-ray diffraction reveals reduced directional growth of ZnO, while Fourier transform infrared spectroscopy confirms PMMA chain bonding with ZnO in PMMA-capped specimens. Scanning electron microscopy illustrates decreased average length and thickness of ZnO nanoplates post-surface modification, indicating a robust interaction between PMMA and ZnO. X-ray photoelectron spectroscopy identifies suppressed defects, including zinc interstitials and oxygen vacancies, affirming ZnO surface capping by PMMA. Absorption spectra display a blue shift in band-edge or increased bandgap, attributed to the combined effects of band alignment offset and reduced oxygen vacancy states. Luminescence spectra show gradual quenching linked to PMMA content increase, with defect-related emission suppression attributed to ZnO surface capping. UV emission suppression is ascribed to donor concentration-dependent Förster resonance energy transfer (FRET) from PMMA to ZnO. Photocatalytic tests reveal enhanced efficiency in PMMA-capped ZnO catalysts attributed to synergies involving charge separation, bulk recombination centers, oxygen vacancy states, and FRET. Efficiency improves with higher PMMA content, aligning with changes in emission intensity. The study demonstrates emission intensities' tunability through surface capping and donor concentration-dependent FRET, ultimately influencing degradation efficiency.